Alcohol compound

ABSTRACT

An alcohol compound of formula (II) in which R 4  represents a methyl group or an ethyl group, R 5  represents a hydrogen atom, and R 6  represents a C 1-3  linear or branched alkyl group. The alcohol compound has physical properties suitable for a material for forming thin films by CVD, and particularly, physical properties suitable for a material for forming metallic-copper thin films.

TECHNICAL FIELD

The present invention relates to a novel metal alkoxide compoundincluding a specific iminoalcohol as a ligand, a thin-film-formingmaterial including the aforementioned compound, a method for producing ametal-containing thin film by using the aforementioned thin-film-formingmaterial, and a novel alcohol compound.

BACKGROUND ART

Thin-film materials including metal elements exhibit variouscharacteristics, such as electric and optical characteristics, and arethus used for a variety of purposes. For example, copper andcopper-containing thin films have the characteristics of highelectroconductivity, high electromigration resistance, and high meltingpoint, and are thus used as LSI wiring materials. Nickel andnickel-containing thin films are mainly used for electronic componentmembers such as resistive films and barrier films, recording mediummembers such as magnetic films, and thin-film solar battery members suchas electrodes. Cobalt and cobalt-containing thin films are used forelectrode films, resistive films, adhesive films, magnetic tapes,carbide tool members, and the like.

Methods for producing such thin films include sputtering, ion plating,metal organic deposition (MOD) methods such as dipping-pyrolysis methodsand sol-gel methods, and chemical vapor deposition. Chemical vapordeposition (also referred to hereinafter simply as CVD), includingatomic layer deposition (ALD), is the most suitable production processbecause of its various advantages, such as that it has excellentcomposition controllability and ability to cover irregularities, issuitable to mass production, and allows hybrid integration.

Various materials have been reported as metal-supplying sources usablein chemical vapor deposition. For example, Patent Literature 1 disclosesa tertiary aminoalkoxide compound of nickel that can be used as anickel-containing thin-film-forming material for MOCVD. PatentLiterature 2 discloses a tertiary aminoalkoxide compound of cobalt thatcan be used as a cobalt-containing thin-film-forming material for MOCVD.Patent Literature 3 discloses a tertiary aminoalkoxide compound ofcopper that can be used as a copper-containing thin-film-formingmaterial for chemical vapor deposition.

CITATION LIST Patent Literature

-   Patent Literature 1: US 2008/171890 A1-   Patent Literature 2: KR 100675983-   Patent Literature 3: JP 2006-328019 A

SUMMARY OF INVENTION Technical Problem

In cases of forming a thin film by vaporizing e.g. a chemical vapordeposition material, a compound (precursor) suitable for such a materialneeds to have such characteristics as that it does not exhibitspontaneous ignitability, has a high vapor pressure and is easy tovaporize, and has high thermal stability. There has been no conventionalmetal compound that can sufficiently satisfy these characteristics.

In cases of forming a metallic-copper thin film by vaporizing e.g. achemical vapor deposition material, there have been such problems asthat the quality of the metallic-copper thin film deteriorates whenheating is performed at temperatures equal to or above 200° C., theelectric resistance value increases, and desired electriccharacteristics cannot be achieved. The cause of these problems has notyet been identified, but it is thought that these problems are caused byan increase in the particle diameter of copper particles existing in theobtained thin film and/or the agglomeration of such particles due toheating at temperatures equal to or above 200° C. So, there has been aneed for a chemical vapor deposition material for formingmetallic-copper thin films that undergoes thermal decomposition attemperatures below 200° C.

The present invention provides a metal alkoxide compound having physicalproperties suitable as a material for forming thin films by CVD, andparticularly provides a metal alkoxide compound having physicalproperties suitable as a material for forming metallic-copper thinfilms.

Solution to Problem

As a result of elaborate investigation, Inventors have found thatspecific metal alkoxide compounds can overcome the aforementionedproblems, thus arriving at the present invention.

The present invention provides a metal alkoxide compound represented bythe following general formula (I), a thin-film-forming materialincluding the same, and a thin film production method for forming ametal-containing thin film by using the aforementioned material.

In the formula, R¹ represents a methyl group or an ethyl group, R²represents a hydrogen atom or a methyl group, R³ represents a C₁₋₃linear or branched alkyl group, M represents a metal atom or a siliconatom, and n represents the valence of the metal atom or silicon atom.

The present invention also provides an alcohol compound that isrepresented by the following general formula (II) and that is suitableas a ligand in the aforementioned metal alkoxide compound.

In the formula, R⁴ represents a methyl group or an ethyl group, R⁵represents a hydrogen atom or a methyl group, and R⁶ represents a C₁₋₃linear or branched alkyl group; if R⁵ is a hydrogen atom, R⁴ representsa methyl group or an ethyl group and R⁶ represents a C₁₋₃ linear orbranched alkyl group; if R⁵ is a methyl group and R⁴ is a methyl group,R⁶ represents a C₃ linear or branched alkyl group; if R⁵ is a methylgroup and R⁴ is an ethyl group, R⁶ represents a C₁₋₃ linear or branchedalkyl group.

Advantageous Effects of Invention

The present invention can provide a novel metal alkoxide compound thatdoes not exhibit spontaneous ignitability, exhibits sufficientvolatility, and has high thermal stability. This metal alkoxide compoundis suitable as a material for forming thin films by CVD. Further, thepresent invention can provide a copper compound that does not exhibitspontaneous ignitability, can be thermally decomposed at temperaturesbelow 200° C., and exhibits sufficient volatility. This copper compoundis suitable as a thin-film-forming material for forming metallic-copperthin films by CVD. The present invention can also provide a novelalcohol compound suitable as a material for the metal alkoxide compoundof the present invention.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic diagram illustrating an example of a chemicalvapor deposition device used for a method for producing ametal-containing thin film according to the present invention.

FIG. 2 is a schematic diagram illustrating another example of a chemicalvapor deposition device used for a method for producing ametal-containing thin film according to the present invention.

FIG. 3 is a schematic diagram illustrating another example of a chemicalvapor deposition device used for a method for producing ametal-containing thin film according to the present invention.

FIG. 4 is a schematic diagram illustrating another example of a chemicalvapor deposition device used for a method for producing ametal-containing thin film according to the present invention.

FIG. 5 is a molecular structure diagram of Compound No. 25 obtained bysingle-crystal X-ray structural analysis.

FIG. 6 is a molecular structure diagram of Compound No. 41 obtained bysingle-crystal X-ray structural analysis.

FIG. 7 is a molecular structure diagram of Compound No. 47 obtained bysingle-crystal X-ray structural analysis.

FIG. 8 is a molecular structure diagram of Compound No. 57 obtained bysingle-crystal X-ray structural analysis.

FIG. 9 is a molecular structure diagram of Compound No. 63 obtained bysingle-crystal X-ray structural analysis.

FIG. 10 is a molecular structure diagram of Compound No. 17 obtained bysingle-crystal X-ray structural analysis.

FIG. 11 is a molecular structure diagram of Compound No. 18 obtained bysingle-crystal X-ray structural analysis.

FIG. 12 is a molecular structure diagram of Compound No. 19 obtained bysingle-crystal X-ray structural analysis.

FIG. 13 is a molecular structure diagram of Compound No. 20 obtained bysingle-crystal X-ray structural analysis.

FIG. 14 is a molecular structure diagram of Compound No. 23 obtained bysingle-crystal X-ray structural analysis.

FIG. 15 is a molecular structure diagram of Compound No. 60 obtained bysingle-crystal X-ray structural analysis.

DESCRIPTION OF EMBODIMENTS

A metal alkoxide compound of the present invention is represented by theaforementioned general formula (I), and is suitable as a precursor for athin-film production method, such as CVD, involving a vaporizing step,and is particularly suitable as a precursor used in ALD because of itshigh thermal stability.

In the aforementioned general formula (I), R¹ represents a methyl groupor an ethyl group, R² represents a hydrogen atom or a methyl group, R³represents a C₁₋₃ linear or branched alkyl group, M represents a metalatom or a silicon atom, and n represents the valence of the metal atomor silicon atom. Examples of the C₁₋₃ linear or branched alkyl grouprepresented by R³ include a methyl group, an ethyl group, a propylgroup, and an isopropyl group. The metal alkoxide compound representedby the aforementioned general formula (I) may exhibit optical activity;the metal alkoxide compound of the present invention, however, is notparticularly differentiated between an R isomer and an S isomer andeither is acceptable, and a mixture including R and S isomers at adiscretionary ratio is also acceptable. A racemic mixture is inexpensiveto produce.

In the aforementioned general formula (I), it is preferable that R¹, R²,and R³ give a high vapor pressure and a high thermal decompositiontemperature in cases of use in a method for producing a thin film otherthan metallic copper and involving a step of vaporizing the compound.More specifically, in cases where M is a metal atom other than copper ora silicon atom, R¹ is preferably a methyl group or an ethyl group, R² ispreferably a hydrogen atom or a methyl group, and R³ is preferably amethyl group, an ethyl group, or an isopropyl group. In cases where M iscopper, R¹ is preferably a methyl group or an ethyl group, R² ispreferably a methyl group, and R³ is preferably a methyl group, an ethylgroup, or an isopropyl group. In cases of a method for producing a thinfilm by MOD, which does not involve a vaporizing step, R¹, R², R³ may beselected discretionarily depending on dissolubility to the solvent used,the thin-film formation reaction, and the like.

In the aforementioned general formula (I), it is preferable that R¹, R²,and R³ give a high vapor pressure and a thermal decompositiontemperature below 200° C. in cases of use in a method for producing ametallic-copper thin film and involving a step of vaporizing thecompound. More specifically, M is copper, R¹ is preferably a methylgroup or an ethyl group, R² is preferably a hydrogen atom, and R³ ispreferably a methyl group, an ethyl group, or an isopropyl group. Amongthe above, a compound wherein R¹ is an ethyl group is particularlypreferable because of its low thermal decomposition temperature. Incases of a method for producing a thin film by MOD, which does notinvolve a vaporizing step, R¹, R², R³ may be selected discretionarilydepending on dissolubility to the solvent used, the thin-film formationreaction, and the like.

In the aforementioned general formula (I), M represents a metal atom ora silicon atom. The metal atom is not particularly limited, and examplesthereof include lithium, sodium, potassium, magnesium, calcium,strontium, barium, titanium, zirconium, hafnium, vanadium, niobium,tantalum, chromium, molybdenum, tungsten, manganese, iron, ruthenium,cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver,gold, zinc, aluminum, gallium, indium, germanium, tin, lead, antimony,bismuth, scandium, yttrium, lanthanum, cerium, praseodymium, neodymium,promethium, samarium, europium, gadolinium, terbium, dysprosium,holmium, erbium, thulium, ytterbium, and lutetium.

The metal alkoxide compound of the present invention is typicallyrepresented by the aforementioned general formula (I), but is notdifferentiated from a case where the end donor group in the ligandcoordinates with the metal atom and forms a ring structure—i.e., a casewhere the compound is represented by the following general formula(I-A)—and the present metal alkoxide compound is a concept encompassingboth.

In the formula, R¹ represents a methyl group or an ethyl group, R²represents a hydrogen atom or a methyl group, R³ represents a C₁₋₃linear or branched alkyl group, M represents a metal atom, and nrepresents the valence of the metal atom.

Concrete examples of metal alkoxide compounds represented by theaforementioned general formula (I) include Compounds Nos. 1 to 16. Itshould be noted that in Compounds Nos. 1 to 16, M is a metal atom or asilicon atom, and n represents the valence of the metal atom or siliconatom.

Specific examples of compounds represented by the aforementioned generalformula (I) include, for example: Compounds Nos. 17 to 32 in cases whereM is copper; Compounds Nos. 33 to 48 where M is nickel; and CompoundsNos. 49 to 64 where M is cobalt.

The metal alkoxide compound of the present invention is not particularlylimited by the production method thereof, and is produced by applyingknown reactions. As an example of the production method, the presentcompound can be obtained by reacting an alkoxide compound, a chloride,an amine compound, or the like, of a metal with an alcohol compoundhaving a corresponding structure.

The thin-film-forming material of the present invention is a materialemploying the above-described metal alkoxide compound of the presentinvention as a precursor for a thin film, and the form of thethin-film-forming material differs depending on the production processto which it is applied. For example, in cases of producing a thin filmincluding only one type of metal or silicon, the thin-film-formingmaterial of the present invention includes no metal compound orsemimetal compound other than the aforementioned metal alkoxidecompound. On the other hand, in cases of producing a thin film includingtwo or more types of metals and/or semimetals, the thin-film-formingmaterial of the present invention includes a compound including thedesired metal(s) and/or a compound including the desired semimetal(s)(referred to hereinafter also as “other precursor”) in addition to theaforementioned metal alkoxide compound.

As described further below, the thin-film-forming material of thepresent invention may further include an organic solvent and/or anucleophilic reagent. As described above, in the thin-film-formingmaterial of the present invention, the physical properties of the metalalkoxide compound, which is the precursor, are suitable for CVD and ALD,and thus, the thin-film-forming material is particularly useful as achemical vapor deposition material (referred to hereinafter also as “CVDmaterial”).

In cases where the thin-film-forming material of the present inventionis a chemical vapor deposition material, the form thereof is chosen asappropriate depending on, for example, the transporting/supplying methodemployed in CVD.

Examples of the aforementioned transporting/supplying method include: agas transportation method in which a CVD material is heated and/ordepressurized in a container for storing the material (also referred tohereinafter simply as “material container”) and vaporized into vapor,and the vapor is introduced, along with a carrier gas—such as argon,nitrogen, or helium—used as necessary, into a deposition chamber(referred to hereinafter also as “deposition reaction unit”) in which asubstrate is placed; and a liquid transportation method in which a CVDmaterial is transported to a vaporizing chamber in a liquid or solutionstate, the material is heated and/or depressurized in the vaporizingchamber and vaporized into vapor, and the vapor is introduced into adeposition chamber. In cases of employing the gas transportation method,the metal alkoxide compound itself represented by the general formula(I) can be used as the CVD material. In cases of employing the liquidtransportation method, the metal alkoxide compound itself represented bythe general formula (I), or a solution obtained by dissolving thecompound in an organic solvent, can be used as the CVD material. The CVDmaterial may further include other precursors, a nucleophilic reagent,or the like.

Further, multi-component CVD methods include: a method in which each ofthe components of the CVD material is vaporized and suppliedindependently (referred to hereinafter also as “single-source method”);and a method in which a mixed material including multi-componentmaterials that have been mixed in advance at a desired composition isvaporized and supplied (referred to hereinafter also as “cocktail-sourcemethod”). In cases of the cocktail-source method, a mixture of the metalalkoxide compound of the present invention and another precursor, or amixed solution in which this mixture is dissolved in an organic solvent,may be used as the CVD material. This mixture or mixed solution mayfurther include a nucleophilic reagent or the like. It should be notedthat, in cases of using only the metal alkoxide compound of the presentinvention as the precursor and employing both R and S isomers, a CVDmaterial including the R isomer and a CVD material including the Sisomer may be vaporized separately, or a CVD material including amixture of the R and S isomers may be vaporized.

As for the aforementioned organic solvent, any generally known organicsolvent may be used without particularly limitation. Examples of theorganic solvent include: acetic esters, such as ethyl acetate, butylacetate, and methoxyethyl acetate; ethers, such as tetrahydrofuran,tetrahydropyran, ethylene glycol dimethyl ether, diethylene glycoldimethyl ether, triethylene glycol dimethyl ether, dibutyl ether, anddioxane; ketones, such as methylbutyl ketone, methylisobutyl ketone,ethylbutyl ketone, dipropyl ketone, diisobutyl ketone, methylamylketone, cyclohexanone, and methylcyclohexanone; hydrocarbons, such ashexane, cyclohexane, methylcyclohexane, dimethylcyclohexane,ethylcyclohexane, heptane, octane, toluene, and xylene;cyano-group-containing hydrocarbons, such as 1-cyanopropane,1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene,1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane,1,4-dicyanocyclohexane, and 1,4-dicyanobenzene; pyridine; and lutidine.Depending on, for example, the dissolubility of the solute and/or therelationship between the usage temperature and the boiling point/flashpoint, the solvent may be used singly, or a mixed solvent including twoor more types of solvents may be used. In cases of using theaforementioned organic solvent(s), it is preferable that the totalamount of precursor(s) in the CVD material, which is a solution in whichthe precursor(s) has/have been dissolved in the organic solvent(s), is0.01 to 2.0 mol/L, and more preferably 0.05 to 1.0 mol/L. The “totalamount of precursor(s)” refers to: the amount of the metal alkoxidecompound of the present invention in cases where the thin-film-formingmaterial of the present invention does not include any metal compound orsemimetal compound other than the metal alkoxide compound of the presentinvention; and the total amount of the metal alkoxide compound of thepresent invention and other precursor(s) in cases where thethin-film-forming material of the present invention includes othermetal-containing compound(s) and/or semimetal-containing compound(s) inaddition to the present metal alkoxide compound.

In cases of employing multi-component CVD, any generally known precursorused as a CVD material may be used without particularly limitation asthe other precursor(s) used with the metal alkoxide compound of thepresent invention.

Examples of other precursors include compounds formed between silicon ora metal and one or more types of compounds selected from a group ofcompounds usable as organic ligands, such as alcohol compounds, glycolcompounds, β-diketone compounds, cyclopentadiene compounds, and organicamine compounds. Examples of metal species in the precursors includelithium, sodium, potassium, magnesium, calcium, strontium, barium,titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium,molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium,iridium, nickel, palladium, platinum, copper, silver, gold, zinc,aluminum, gallium, indium, germanium, tin, lead, antimony, bismuth,scandium, yttrium, lanthanum, cerium, praseodymium, neodymium,promethium, samarium, europium, gadolinium, terbium, dysprosium,holmium, erbium, thulium, ytterbium, and lutetium.

Examples of alcohol compounds usable as organic ligands in theaforementioned other precursors include: alkyl alcohols, such asmethanol, ethanol, propanol, isopropyl alcohol, butanol, secondary butylalcohol, isobutyl alcohol, tertiary butyl alcohol, pentyl alcohol,isopentyl alcohol, and tertiary pentyl alcohol; ether alcohols, such as2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol,2-(2-methoxyethoxy)ethanol, 2-methoxy-1-methylethanol,2-methoxy-1,1-dimethylethanol, 2-ethoxy-1,1-dimethylethanol,2-isopropoxy-1,1-dimethylethanol, 2-butoxy-1,1-dimethylethanol,2-(2-methoxyethoxy)-1,1-dimethylethanol, 2-propoxy-1,1-diethylethanol,2-s-butoxy-1,1-diethylethanol, and 3-methoxy-1,1-dimethylpropanol; anddialkylaminoalcohols, such as dimethylaminoethanol,ethylmethylaminoethanol, diethylaminoethanol, dimethylamino-2-pentanol,ethylmethylamino-2-pentanol, dimethylamino-2-methyl-2-pentanol,ethylmethylamino-2-methyl-2-pentanol, anddiethylamino-2-methyl-2-pentanol.

Examples of glycol compounds usable as organic ligands in theaforementioned other precursors include 1,2-ethanediol, 1,2-propanediol,1,3-propanediol, 2,4-hexanediol, 2,2-dimethyl-1,3-propanediol,2,2-diethyl-1,3-propanediol, 1,3-butanediol, 2,4-butanediol,2,2-diethyl-1,3-butanediol, 2-ethyl-2-butyl-1,3-propanediol,2,4-pentanediol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol,2,4-hexanediol, and 2,4-dimethyl-2,4-pentanediol.

Examples of β-diketone compounds include: alkyl-substituted β-diketones,such as acetylacetone, hexane-2,4-dione, 5-methylhexane-2,4-dione,heptane-2,4-dione, 2-methylheptane-3,5-dione, 5-methylheptane-2,4-dione,6-methylheptane-2,4-dione, 2,2-dimethylheptane-3,5-dione,2,6-dimethylheptane-3,5-dione, 2,2,6-trimethylheptane-3,5-dione,2,2,6,6-tetramethylheptane-3,5-dione, octane-2,4-dione,2,2,6-trimethyloctane-3,5-dione, 2,6-dimethyloctane-3,5-dione,2,9-dimethylnonane-4,6-dione, 2-methyl-6-ethyldecane-3,5-dione, and2,2-dimethyl-6-ethyldecane-3,5-dione; fluorine-substituted alkylβ-diketones, such as 1,1,1-trifluoropentane-2,4-dione,1,1,1-trifluoro-5,5-dimethylhexane-2,4-dione,1,1,1,5,5,5-hexafluoropentane-2,4-dione, and1,3-diperfluorohexylpropane-1,3-dione; and ether-substitutedβ-diketones, such as 1,1,5,5-tetramethyl-1-methoxyhexane-2,4-dione,2,2,6,6-tetramethyl-1-methoxyheptane-3,5-dione, and2,2,6,6-tetramethyl-1-(2-methoxyethoxy)heptane-3,5-dione.

Examples of cyclopentadiene compounds include cyclopentadiene,methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene,isopropylcyclopentadiene, butylcyclopentadiene, secondarybutylcyclopentadiene, isobutylcyclopentadiene, tertiarybutylcyclopentadiene, dimethylcyclopentadiene, andtetramethylcyclopentadiene. Examples of organic amine compounds usableas the aforementioned organic ligands include methylamine, ethylamine,propylamine, isopropylamine, butylamine, secondary butylamine, tertiarybutylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine,diisopropylamine, ethylmethylamine, propylmethylamine, andisopropylmethylamine.

The aforementioned other precursors are known in this technical field,and methods for producing the same are also known. An example of amethod for producing a precursor is as follows. For example, in cases ofusing an alcohol compound as an organic ligand, a precursor can beproduced by reacting an inorganic salt of the aforementioned metal or ahydrate thereof with an alkali metal alkoxide of the alcohol compound.Examples of an inorganic salt of metal or a hydrate thereof may includea halide or a nitrate of the metal. Examples of an alkali metal alkoxidemay include sodium alkoxide, lithium alkoxide, and potassium alkoxide.

In cases of employing the single-source method, the other precursor ispreferably a compound that has a thermal and/or oxidative decompositionbehavior similar to that of the metal alkoxide compound of the presentinvention. In cases of employing the cocktail-source method, the otherprecursor is preferably a compound that does not undergo alteration dueto chemical reaction etc. at the time of mixing, in addition to having athermal and/or oxidative decomposition behavior similar to that of thepresent metal alkoxide compound.

Of the aforementioned other precursors, examples of precursors includingtitanium, zirconium, or hafnium include compounds represented by thefollowing general formulas (II-1) to (II-5).

In the formula, M¹ represents titanium, zirconium, or hafnium, R^(a) andR^(b) each independently represent a C₁₋₂₀ alkyl group that may besubstituted by a halogen atom and that may include an oxygen atom in itschain, R^(c) represents a C₁₋₈ alkyl group, R^(d) represents a C₂₋₁₈alkylene group that may be branched, R^(e) and R^(f) each independentlyrepresent a hydrogen atom or a C₁₋₃ alkyl group, R^(g), R^(h), R^(k),and R^(j) each independently represent a hydrogen atom or a C₁₋₄ alkylgroup, p represents an integer of 0 to 4, q represents 0 or 2, rrepresents an integer of 0 to 3, s represents an integer of 0 to 4, andt represents an integer of 1 to 4.)

In the formulas (II-1) to (II-5), examples of the C₁₋₂₀ alkyl group thatmay be substituted by a halogen atom and that may include an oxygen atomin its chain, as represented by R^(a) and R^(b), include methyl, ethyl,propyl, isopropyl, butyl, secondary butyl, tertiary butyl, isobutyl,amyl, isoamyl, secondary amyl, tertiary amyl, hexyl, cyclohexyl,1-methylcyclohexyl, heptyl, 3-heptyl, isoheptyl, tertiary heptyl,n-octyl, isooctyl, tertiary octyl, 2-ethylhexyl, trifluoromethyl,perfluorohexyl, 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl,2-(2-methoxyethoxy)ethyl, 1-methoxy-1,1-dimethylmethyl,2-methoxy-1,1-dimethylethyl, 2-ethoxy-1,1-dimethylethyl,2-isopropoxy-1,1-dimethylethyl, 2-butoxy-1,1-dimethylethyl, and2-(2-methoxyethoxy)-1,1-dimethylethyl. Examples of the C₁₋₈ alkyl grouprepresented by R^(c) include methyl, ethyl, propyl, isopropyl, butyl,secondary butyl, tertiary butyl, isobutyl, amyl, isoamyl, secondaryamyl, tertiary amyl, hexyl, 1-ethylpentyl, cyclohexyl,1-methylcyclohexyl, heptyl, isoheptyl, tertiary heptyl, n-octyl,isooctyl, tertiary octyl, and 2-ethylhexyl. The C₂₋₁₈ alkylene groupthat may be branched, as represented by R^(d), is a group resulting froma glycol, and examples of such a glycol include 1,2-ethanediol,1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 2,4-hexanediol,2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol,2,2-diethyl-1,3-butanediol, 2-ethyl-2-butyl-1,3-propanediol,2,4-pentanediol, 2-methyl-1,3-propanediol, and 1-methyl-2,4-pentanediol.Examples of the C₁₋₃ alkyl group represented by R^(e) and R^(f) includemethyl, ethyl, propyl, and 2-propyl. Examples of the C₁₋₄ alkyl grouprepresented by R^(g), R^(h), R^(j), and R^(k) include methyl, ethyl,propyl, isopropyl, butyl, secondary butyl, tertiary butyl, and isobutyl.

Concrete examples of titanium-containing precursors include:tetrakis-alkoxy titanium, such as tetrakis(ethoxy)titanium,tetrakis(2-propoxy)titanium, tetrakis(butoxy)titanium,tetrakis(secondary butoxy)titanium, tetrakis(isobutoxy)titanium,tetrakis(tertiary butoxy)titanium, tetrakis(tertiary amyl)titanium, andtetrakis(1-methoxy-2-methyl-2-propoxy)titanium; tetrakis β-diketonatotitanium, such as tetrakis(pentane-2,4-dionato)titanium,(2,6-dimethylheptane-3,5-dionato)titanium, andtetrakis(2,2,6,6-tetramethylheptane-3,5-dionato)titanium;bis(alkoxy)bis(β-diketonato)titanium, such asbis(methoxy)bis(pentane-2,4-dionato)titanium,bis(ethoxy)bis(pentane-2,4-dionato)titanium, bis(tertiarybutoxy)bis(pentane-2,4-dionato)titanium,bis(methoxy)bis(2,6-dimethylheptane-3,5-dionato)titanium,bis(ethoxy)bis(2,6-dimethylheptane-3,5-dionato)titanium,bis(2-propoxy)bis(2,6-dimethylheptane-3,5-dionato)titanium, bis(tertiarybutoxy)bis(2,6-dimethylheptane-3,5-dionato)titanium, bis(tertiaryamyloxy)bis(2,6-dimethylheptane-3,5-dionato)titanium,bis(methoxy)bis(2,2,6,6-tetramethylheptane-3,5-dionato)titanium,bis(ethoxy)bis(2,2,6,6-tetramethylheptane-3,5-dionato)titanium,bis(2-propoxy)bis(2,6,6,6-tetramethylheptane-3,5-dionato)titanium,bis(tertiary butoxy)bis(2,2,6,6-tetramethylheptane-3,5-dionato)titanium,and bis(tertiaryamyloxy)bis(2,2,6,6-tetramethylheptane-3,5-dionato)titanium; glycoxybis(β-diketonato)titanium, such as (2-methylpentanedioxy)bis(2,2,6,6-tetramethylheptane-3,5-dionato)titanium, and(2-methylpentane dioxy)bis(2,6-dimethylheptane-3,5-dionato)titanium;(cyclopentadienyl)tris(dialkylamino)titanium, such as(methylcyclopentadienyl)tris(dimethylamino)titanium,(ethylcyclopentadienyl)tris(dimethylamino)titanium,(cyclopentadienyl)tris(dimethylamino)titanium,(methylcyclopentadienyl)tris(ethylmethylamino)titanium,(ethylcyclopentadienyl)tris(ethylmethylamino)titanium,(cyclopentadienyl)tris(ethylmethylamino)titanium,(methylcyclopentadienyl)tris(diethylamino)titanium,(ethylcyclopentadienyl)tris(diethylamino)titanium, and(cyclopentadienyl)tris(diethylamino)titanium; and(cyclopentadienyl)tris(alkoxy)titanium, such as(cyclopentadienyl)tris(methoxy)titanium,(methylcyclopentadienyl)tris(methoxy)titanium,(ethylcyclopentadienyl)tris(methoxy)titanium,(propylcyclopentadienyl)tris(methoxy)titanium,(isopropylcyclopentadienyl)tris(methoxy)titanium,(butylcyclopentadienyl)tris(methoxy)titanium,(isobutylcyclopentadienyl)tris(methoxy)titanium, and (tertiarybutylcyclopentadienyl)tris(methoxy)titanium. Examples ofzirconium-containing precursors or hafnium-containing precursors includecompounds in which the titanium in the aforementioned compounds given asexamples of the titanium-containing precursors is substituted byzirconium or hafnium.

Examples of precursors containing a rare-earth element include compoundsrepresented by the following formulas (III-1) to (III-3).

In the formula, M² represents a rare-earth atom, R^(a) and R^(b) eachindependently represent a C₁₋₂₀ alkyl group that may be substituted by ahalogen atom and that may include an oxygen atom in its chain, R^(c)represents a C₁₋₈ alkyl group, R^(e) and R^(f) each independentlyrepresent a hydrogen atom or a C₁₋₃ alkyl group, R^(g) and R^(j) eachindependently represent a C₁₋₄ alkyl group, p′ represents an integer of0 to 3, and r′ represents an integer of 0 to 2.

In the aforementioned precursor containing a rare-earth element,examples of the rare-earth atom represented by M² include scandium,yttrium, lanthanum, cerium, praseodymium, neodymium, promethium,samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium,thulium, ytterbium, and lutetium, and examples of groups represented byR^(a), R^(b), R^(c), R^(e), R^(f), R^(g), and R^(j) include groups givenas examples for the aforementioned titanium precursors.

Further, the thin-film-forming material of the present invention mayinclude, as necessary, a nucleophilic reagent for imparting stability tothe metal alkoxide compound of the present invention and the otherprecursors. Examples of such nucleophilic reagents include: ethyleneglycol ethers, such as glyme, diglyme, triglyme, and tetraglyme; crownethers, such as 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8,dicyclohexyl-24-crown-8, and dibenzo-24-crown-8; polyamines, such asethylenediamine, N,N′-tetramethylethylenediamine, diethylenetriamine,triethylenetetramine, tetraethylene pentamine, pentaethylene hexamine,1,1,4,7,7-pentamethyldiethylenetriamine,1,1,4,7,10,10-hexamethyltriethylenetetramine, and triethoxytriethyleneamine; cyclic polyamines, such as cyclam and cyclen; heterocyclecompounds, such as pyridine, pyrrolidine, piperidine, morpholine,N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine,tetrahydrofuran, tetrahydropyran, 1,4-dioxane, oxazole, thiazole, andoxathiolane; β-keto esters, such as methyl acetoacetate, ethylacetoacetate, and 2-methoxyethyl acetoacetate; and β-diketones, such asacetylacetone, 2,4-hexane dione, 2,4-heptane dione, 3,5-heptane dione,and dipivaloylmethane. The amount of nucleophilic reagent(s) used withrespect to 1 mol of the total amount of precursor(s) is preferably from0.1 mol to 10 mol, and more preferably from 1 to 4 mol.

The thin-film-forming material of the present invention is made suchthat components, such as metal element impurities, halogen impuritiessuch as chlorine impurities, and organic impurities, other than thecomponents constituting the thin-film-forming material are excluded asmuch as possible. As for metal element impurities, the amount perelement is preferably 100 ppb or less, more preferably 10 ppb or less,and the total amount is preferably 1 ppm or less, and more preferably100 ppb or less. Particularly, in cases where the material is used forLSI gate insulating films, gate films, or barrier layers, it isnecessary to minimize the content of alkali metal elements,alkaline-earth metal elements, and congeneric elements, which affect theelectric characteristics of the obtained thin films. The amount ofhalogen impurities is preferably 100 ppm or less, and more preferably 10ppm or less, and even more preferably 1 ppm or less. The total amount oforganic impurities is preferably 500 ppm or less, more preferably 50 ppmor less, and even more preferably 10 ppm or less. Moisture causes thegeneration of particles in the chemical vapor deposition material andthe generation of particles during the formation of a thin film, andthus, as for metal compounds, organic solvents, and nucleophilicreagents, it is better to remove as much moisture as possible in advanceat the time of use in order to reduce the moisture in each component.The moisture content in each metal compound, organic solvent, ornucleophilic reagent is preferably 10 ppm or less, and more preferably 1ppm or less.

Further, in order to reduce or prevent particle contamination of thethin film being formed, it is preferable that particles are excluded asmuch as possible from the thin-film-forming material of the presentinvention. More specifically, according to particle measurement by alight-scattering liquid-borne particle detector in a liquid phase, it ispreferable that the number of particles larger than 0.3 μm is 100 orfewer in 1 ml of the liquid phase, and more preferably, the number ofparticles larger than 0.2 μm is 1000 or fewer in 1 ml of the liquidphase, and even more preferably, the number of particles larger than 0.2μm is 100 or fewer in 1 ml of the liquid phase.

The thin-film production method of the present invention for producing athin film by using a thin-film-forming material of the present inventionfollows the CVD method involving: introducing, into a deposition chamberin which a substrate is placed, a vapor obtained by vaporizing thethin-film-forming material of the present invention and a reactive gaswhich is used if necessary; and growing and depositing ametal-containing thin film on the surface of the substrate bydecomposing and/or chemically reacting the precursor on the substrate.Generally known conditions and methods can be used without particularlylimitation for the method for transporting/supplying the material, thedeposition method, production conditions, the production device, etc.

Examples of the reactive gas which is used if necessary include:oxidizing gases, such as oxygen, ozone, nitrogen dioxide, nitric oxide,water vapor, hydrogen peroxide, formic acid, acetic acid, and aceticanhydride; reducing gases, such as hydrogen; and gases that produce anitride, such as hydrazine, ammonia, and organic amine compounds such asmonoalkylamine, dialkylamine, trialkylamine, and alkylene diamine. Oneor more types of gases may be used.

Examples of the transporting/supplying method include the gastransportation method, the liquid transportation method, thesingle-source method, and the cocktail-source method, as describedabove.

Examples of the deposition method include: thermal CVD in which a thinfilm is deposited by causing reaction of a material gas, or a materialgas and a reactive gas, only by heat; plasma CVD that uses heat and aplasma; optical CVD that uses heat and light; optical plasma CVD thatuses heat, light, and a plasma; and ALD in which the deposition reactionin CVD is divided into elementary processes, and deposition is performedstepwise on a molecular level.

Examples of the material for the substrate include: silicon; ceramics,such as silicon nitride, titanium nitride, tantalum nitride, titaniumoxide, titanium nitride, ruthenium oxide, zirconium oxide, hafniumoxide, and lanthanum oxide; glass; and metals such as metallicruthenium. The shape of the substrate may be, for example, plate-like,spherical, fibrous, or squamous. The surface of the substrate may beplanar, or may have a three-dimensional structure such as a trenchstructure.

The aforementioned production conditions include, for example, reactiontemperature (substrate temperature), reaction pressure, deposition rate,etc. The reaction temperature is preferably higher than or equal to 100°C., which is the temperature at which the metal alkoxide compound of thepresent invention reacts sufficiently, and is more preferably from 150°C. to 400° C. In cases of thermal CVD and optical CVD, the reactionpressure is preferably from atmospheric pressure to 10 Pa, and in casesof using a plasma, the reaction pressure is preferably from 2000 Pa to10 Pa.

The deposition rate can be controlled by the material supplyingconditions (vaporizing temperature, vaporizing pressure), the reactiontemperature, and the reaction pressure. A high deposition rate mayimpair the characteristics of the obtained thin film, whereas a lowdeposition rate may cause problems in productivity. Thus, the depositionrate is preferably from 0.01 to 100 nm/minute, and more preferably from1 to 50 nm/minute. In cases of ALD, the deposition rate is controlled bythe number of cycles so that a desired film thickness can be obtained.

Other production conditions include the temperature and pressure at thetime of vaporizing the thin-film-forming material into vapor. The stepfor vaporizing the thin-film-forming material into vapor may beperformed inside the material container or inside the vaporizingchamber. In either case, it is preferable to evaporate thethin-film-forming material of the present invention at a temperaturefrom 0 to 150° C. Further, in cases of vaporizing the thin-film-formingmaterial into vapor inside the material container or the vaporizingchamber, the pressure inside the material container and the pressureinside the vaporizing chamber are both preferably from 1 to 10000 Pa.

The thin-film production method of the present invention employs ALD,and involves a material introduction step of vaporizing thethin-film-forming material into vapor and introducing the vapor into adeposition chamber according to the aforementionedtransporting/supplying method, and may also involve: aprecursor-thin-film deposition step of forming a precursor thin film onthe surface of the substrate by the metal alkoxide compound in thevapor; a gas discharge step of discharging unreacted metal alkoxidecompound gas; and a metal-containing-thin-film formation step of forminga metal-containing thin film on the surface of the substrate bychemically reacting the precursor thin film with a reactive gas.

Below, each of the aforementioned steps will be described in detailaccording to an example of forming a metal-oxide thin film. In cases offorming a metal-oxide thin film by ALD, first the aforementionedmaterial introduction step is performed. The temperature and pressurepreferred for making the thin-film-forming material into a vapor are asdescribed above. Next, a precursor thin film is deposited on thesubstrate surface by the metal alkoxide compound introduced into adeposition reaction unit (precursor-thin-film deposition step). At thistime, heat may be applied by heating the substrate or heating thedeposition reaction unit. The precursor thin film deposited in this stepis a metal-oxide thin film, or a thin film produced by the decompositionand/or reaction of a portion of the metal alkoxide compound, and has adifferent composition from the intended metal-oxide thin film. Thesubstrate temperature during this step is preferably from roomtemperature to 500° C., and more preferably from 150 to 350° C. Thepressure in the system (inside the deposition chamber) during this stepis preferably from 1 to 10000 Pa, and more preferably from 10 to 1000Pa.

Next, unreacted metal alkoxide compound gas and by-product gas aredischarged from the deposition reaction unit (discharge step). It isideal to completely discharge the unreacted metal alkoxide compound gasand by-product gas from the deposition reaction unit, but completedischarge is not absolutely necessary. Discharging methods include:purging the gases from the system by an inert gas such as nitrogen,helium, or argon; discharging the gases by depressurizing the inside ofthe system; and methods in which the above are combined. In cases ofdepressurization, the degree of depressurization is preferably from 0.01to 300 Pa, and more preferably from 0.01 to 100 Pa.

Next, an oxidizing gas is introduced into the deposition reaction unit,and by the action of the oxidizing gas, or the oxidizing gas and heat, ametal-oxide thin film is formed from the precursor thin film obtained inthe previous precursor-thin-film deposition step (metal-oxide-containingthin-film formation step). The temperature for causing the action ofheat in the present step is preferably from room temperature to 500° C.,and more preferably from 150 to 350° C. The pressure in the system(inside the deposition chamber) during this step is preferably from 1 to10000 Pa, and more preferably from 10 to 1000 Pa. The metal alkoxidecompound of the present invention has good reactivity with oxidizinggases, and can produce metal-oxide thin films.

In cases of employing ALD as described above in the thin-film productionmethod of the present invention, thin-film deposition achieved by aseries of operations—including the aforementioned material introductionstep, precursor-thin-film deposition step, discharge step, andmetal-oxide-containing thin-film formation step—is considered as asingle cycle, and this cycle may be repeated a plurality of times untila thin film with the necessary film thickness is obtained. In this case,it is preferable that unreacted metal alkoxide compound gas, reactivegas (oxidizing gas in cases of forming a metal-oxide thin film), andby-product gas are discharged after each cycle as in the aforementioneddischarge step, and then the next cycle is performed.

In the formation of metal-oxide thin films by ALD, energy such asplasma, light, or voltage may be applied, and also, a catalyst may beused. The timing for applying such energy and the timing for using thecatalyst are not particularly limited, and for example, the timing maybe: at the time of introducing a metal alkoxide compound gas in thematerial introduction step; at the time of heating in theprecursor-thin-film deposition step or the metal-oxide-containingthin-film formation step; at the time of discharging gas from the systemin the discharge step; at the time of introducing an oxidizing gas inthe metal-oxide-containing thin-film formation step; or between theaforementioned steps.

Further, in the thin-film production method of the present invention, inorder to obtain even better electric characteristics, it is possible toperform an annealing treatment in an inert atmosphere, an oxidizingatmosphere, or a reducing atmosphere, after thin-film deposition. Incases where steps need embedding, a reflow step may be provided; in thiscase, the temperature is from 200 to 1000° C., and preferably from 250to 500° C.

A known chemical vapor deposition device can be used as the device forproducing thin films by using the thin-film-forming material of thepresent invention. Concrete examples of such devices include: a devicethat can supply a precursor by bubbling, as illustrated in FIG. 1; adevice having a vaporizing chamber, as illustrated in FIG. 2; anddevices capable of subjecting a reactive gas to a plasma treatment, asillustrated in FIGS. 3 and 4. The device is not limited tosingle-substrate devices such as those illustrated in FIGS. 1, 2, 3, and4, and it is possible to use a device that can simultaneously treat aplurality of substrates by using a batch furnace.

The thin film produced by using the thin-film-forming material of thepresent invention may be made as a desired type of thin film, such asmetal, oxide ceramic, nitride ceramic, or glass, by appropriatelyselecting the other precursor(s), the reactive gas, and the productionconditions. Such thin films are known to exhibit variouscharacteristics, such as electric and optical characteristics, and arethus used for a variety of purposes. For example, copper andcopper-containing thin films have the characteristics of highelectroconductivity, high electromigration resistance, and high meltingpoint, and are thus used as LSI wiring materials. Nickel andnickel-containing thin films are mainly used for electronic componentmembers such as resistive films and barrier films, recording mediummembers such as magnetic films, and thin-film solar battery members suchas electrodes. Cobalt and cobalt-containing thin films are used forelectrode films, resistive films, adhesive films, magnetic tapes,carbide tool members, and the like.

An alcohol compound of the present invention is represented by theaforementioned general formula (II), and is a compound particularlysuitable as a ligand in a compound that is suitable as a precursor in athin-film production method involving a vaporizing step, such as CVD.

In the aforementioned general formula (II), R⁴ represents a methyl groupor an ethyl group, R⁵ represents a hydrogen atom or a methyl group, andR⁶ represents a C₁₋₃ linear or branched alkyl group. Examples of theC₁₋₃ linear or branched alkyl group represented by R⁶ include a methylgroup, an ethyl group, a propyl group, and an isopropyl group. Note,however, that if R⁵ is a hydrogen atom, R⁴ represents a methyl group oran ethyl group and R⁶ represents a C₁₋₃ linear or branched alkyl group.If R⁵ is a methyl group and R⁴ is a methyl group, R⁶ represents a C₃linear or branched alkyl group. If R⁵ is a methyl group and R⁴ is anethyl group, R⁶ represents a C₁₋₃ linear or branched alkyl group.

The alcohol compound of the present invention may have optical isomers,but is not differentiated by optical isomerism.

Concrete examples of the alcohol compound of the present inventioninclude the following Compounds Nos. 65 to 78.

The alcohol compound of the present invention is not particularlylimited by the production method thereof, and can be obtained, forexample, by reacting an alkylene oxide compound, water, and analkylamine compound under suitable conditions, performing extractionwith a suitable solvent, and performing a dehydration treatment.

The alcohol compound of the present invention can be used as a ligand ina metal compound used as a thin-film-forming material or the like, andparticularly, an alcohol compound wherein R⁵ in the general formula (II)is hydrogen can be used as a ligand in a copper compound that isextremely useful as a material for forming a metallic-copper thin film.The alcohol compound of the present invention can also be used, forexample, as synthetic materials for solvents, perfumes, agrochemicals,pharmaceuticals, and various polymers.

EXAMPLES

The present invention is described in further detail below according toworking examples, production examples, comparative examples, andevaluation examples. The present invention, however, is not limitedwhatsoever by the following examples etc.

Examples 1 to 7 are production examples each for producing an alcoholcompound of the present invention used as a material for a metalalkoxide compound of the present invention. Production Example 1 is anexample for producing an alcohol compound used as a material for a metalalkoxide compound of the present invention. Examples 8 to 18 areproduction examples each for producing a metal alkoxide compound of thepresent invention.

Examples 19 and 20 are production examples each for producing ametallic-copper or copper-oxide thin film by using a metal alkoxidecompound (copper compound) of the present invention. Comparative Example1 is a production example for producing a metallic-copper thin film byusing a comparative metal alkoxide compound (copper compound).

Evaluation Example 1 evaluates the physical properties (thermalstability) of metal alkoxide compounds of the present invention producedaccording to Examples 8 to 12 and of comparative compounds havingstructures similar to the present invention.

Evaluation Example 2 evaluates the physical properties (thermalstability) of metal alkoxide compounds (copper compounds) of the presentinvention produced according to Examples 13 to 15 and 17 and of acomparative compound having a structure similar to the presentinvention.

Evaluation Example 3 evaluates the physical properties ofmetallic-copper thin films produced according to Example 20 andComparative Example 1.

Example 1

Production of Alcohol Compound (Compound No. 65) of Present Invention:

To a reaction flask were added 100 ml of diethyl ether and 45.5 g of1-methoxy-2-methylpropylene oxide, and the mixture was stirred over anice-cooled bath and cooled to around 0° C. Further, 50.0 g of water wasadded slowly dropwise over a period of 30 minutes, and the mixture wasstirred for 15 minutes. Then, 45.0 g of a 40% methylamine aqueoussolution was added slowly dropwise over a period of 30 minutes whilecooling on ice, the mixture was stirred for 30 minutes, returned to roomtemperature, and subjected to reaction for about 20 hours. Then,extraction was performed with 300 ml of diethyl ether, and the obtainedorganic layer was subjected to a dehydration treatment by magnesiumsulfate and a molecular sieve 4A. The molecular weight of the obtainedcompound was measured with a gas chromatograph mass spectrometer (may beabbreviated as GC-MS below). Also, an elementary analysis of theobtained compound was performed. These analysis values are indicated in(1) and (2) below. From these results, it was verified that the obtainedcompound was Compound No. 65. Note that the yield of the compound was45%.

Analysis Values:

(1) GC-MS m/z: 101 (M+)

(2) Elementary Analysis: C: 59.0 mass %; H: 11.5 mass %; O: 15.2 mass %;N: 14.3 mass % (theoretical values: C: 59.4%; H: 10.9%; O: 15.8%; N:13.9%).

Example 2

Production of Alcohol Compound (Compound No. 66) of Present Invention:

To a reaction flask was added 20.0 g of1,1-dimethoxy-2-methylbutane-2-ol, and a solution made by mixing 20 g ofwater and 0.8 ml of a 36% hydrochloric acid was added slowly dropwise tothe reaction flask over a period of 30 minutes at room temperature, andthe mixture was stirred for about 60 hours. Then, 31.4 g of a 40%methylamine aqueous solution was added slowly dropwise over a period of30 minutes while cooling on ice, the mixture was returned to roomtemperature, and was subjected to reaction for 3 hours. Then, extractionwas performed with 80 ml of toluene, and the obtained organic layer wassubjected to a dehydration treatment with magnesium sulfate and amolecular sieve 4A. The molecular weight of the obtained compound wasmeasured with a GC-MS. Also, an elementary analysis of the obtainedcompound was performed. These analysis values are indicated in (1) and(2) below. From these results, it was verified that the obtainedcompound was Compound No. 66. Note that the yield of the compound was54%.

Analysis Values:

(1) GC-MS m/z: 115 (M+)

(2) Elementary Analysis: C: 63.0 mass %; H: 10.8 mass %; O: 13.5 mass %;N: 12.6 mass % (theoretical values: C: 62.6%; H: 11.3%; O: 13.9%; N:12.2%).

Example 3

Production of Alcohol Compound (Compound No. 67) of Present Invention:

To a reaction flask were added 30 g of diethyl ether and 2.5 g of water,and the mixture was stirred over an ice-cooled bath and cooled to around0° C. Then, 2.5 g of 1-methoxy-2-methylpropylene oxide was added slowlydropwise to the reaction flask over a period of 5 minutes, and themixture was stirred for 15 minutes. Then, 4.4 g of a 33% ethylamineaqueous solution was added slowly dropwise over a period of 10 minuteswhile cooling on ice, the mixture was stirred for 30 minutes, returnedto room temperature, and subjected to reaction for about 20 hours. Then,extraction was performed with 50 ml of diethyl ether, and the obtainedorganic layer was subjected to a dehydration treatment with magnesiumsulfate and a molecular sieve 4A. The molecular weight of the obtainedcompound was measured with a GC-MS. Also, an elementary analysis of theobtained compound was performed. These analysis values are indicated in(1) and (2) below. From these results, it was verified that the obtainedcompound was Compound No. 67. Note that the yield of the compound was52%.

Analysis Values:

(1) GC-MS m/z: 115 (M+)

(2) Elementary Analysis: C: 62.9 mass %; H: 11.0 mass %; O: 14.6 mass %;N: 11.9 mass % (theoretical values: C: 62.6%; H: 11.3%; O: 13.9%; N:12.2%).

Example 4

Production of Alcohol Compound (Compound No. 71) of Present Invention:

In a reaction flask, a mixed solution of 30 g of diethyl ether and 2.5 gof water was stirred while cooling on ice, and the solution temperaturewas cooled to 10° C. To this reaction flask, 2.5 g of1-methoxy-2-methylpropylene oxide was added dropwise at the sametemperature, and the mixture was stirred for 30 minutes. Then,isopropylamine was added dropwise at the same temperature while coolingon ice, and the mixture was stirred for 30 minutes. Then, the mixturewas returned to room temperature and stirred for 8 hours. A suitableamount of magnesium sulfate was added to adsorb the water in thesolution, and the solution was filtered. A sufficiently dried molecularsieve 4A was added to the filtrate to completely dehydrate the filtrate.The molecular weight of the obtained compound was measured with a GC-MS.Also, an elementary analysis of the obtained compound was performed.These analysis values are indicated in (1) and (2) below. From theseresults, it was verified that the obtained compound was Compound No. 71.Note that the yield of the compound was 51%.

Analysis Values:

(1) GC-MS m/z: 129 (M+)

(2) Elementary Analysis: C: 64.8 mass %; H: 11.3 mass %; O: 12.9 mass %;N: 11.2 mass % (theoretical values: C: 65.1%; H: 11.6%; O: 12.4%; N:10.9%).

Example 5

Production of Alcohol Compound (Compound No. 74) of Present Invention:

To a reaction flask were added 27.1 g of 3-hydroxy-3-methyl-2-butanone,33.1 g of methanol, and a molecular sieve 4A, and the mixture wasstirred at room temperature. To this reaction flask, 23.2 g ofisopropylamine was added slowly dropwise at room temperature. Aftercompletion of this dropwise addition, the mixture was stirred for 6hours at room temperature. Then, stirring was stopped, 7.93 g of amolecular sieve 4A was added, and the mixture was left still for 15hours at room temperature. Then, the mixture was filtered, and thefiltrate was fractionated. Methanol was removed by evaporation from thefractionated filtrate. The liquid residue was distilled under reducedpressure at a pressure of 3.8 kPa and a fraction temperature of 62° C.The yielded amount of the obtained compound was 10.4 g, and the yieldwas 27%. The molecular weight of the obtained compound was measured witha GC-MS. Further, ¹H-NMR of the obtained compound was measured, andelementary analysis was performed. These analysis values are indicatedin (1), (2), and (3) below. From these results, it was verified that theobtained compound was Compound No. 74.

Analysis Values:

(1) ¹H-NMR (solvent: deuterated benzene) (chemical shift: multiplicity:number of H): (5.996:t:1), (3.332:m: 1), (1.329:t:3), (1.232:s:6),(0.967:d:6).

(2) GC-MS m/z: 144 (M+)

(3) Elementary Analysis: C: 67.6 mass %; H: 12.3 mass %; O: 10.8 mass %;N: 9.5 mass % (theoretical values: C: 67.1%; H: 11.9%; O: 11.2%; N:9.8%).

Example 6

Production of Alcohol Compound (Compound No. 68) of Present Invention:

To a reaction flask was added a tetrahydrofuran solution ofethylmagnesium bromide (7.4%, 440 g), and this was stirred over anice-cooled bath and cooled to around 0° C. To this solution, pyruvicaldehyde dimethylacetal (30 g) was added dropwise over a period of 30minutes, and the solution was subjected to a Grignard reaction. Then,the solution was returned to room temperature, and was subjected toreaction for 12 hours. The reaction solution was cooled on ice and wasquenched by adding dropwise 300 g of a 17% ammonium chloride aqueoussolution, and then, the solution was transferred to a separatory funnelto separate organic matters, and was dehydrated with a suitable amountof magnesium sulfate. After filtering the organic layer, this wasdesolventized at around 80° C. in an oil bath under reduced pressure.Then, distillation was performed in an oil bath at around 85° C. underreduced pressure, and at a column top temperature of 49° C., 20 g ofcolorless, transparent 1,1-dimethoxy-2-methylbutane-2-ol was obtained.To 20 g of this 1,1-dimethoxymethylbutane-2-ol, 40 g of pure water and2.5 g of a 36% hydrochloric acid were added while cooling on ice, andthe mixture was stirred overnight. Then, 74 g of a 33% ethylamineaqueous solution was added dropwise while cooling on ice, and themixture was subjected to reaction for 10 hours. At this time, the pH ofthe reaction solution was from 10 to 11. In order to recover the targetproduct dissolved in the aqueous solution, 150 g of toluene was added tothe reaction solution, and the organic layer was extracted and separatedwith a separatory funnel, was dehydrated with magnesium sulfate, and wasfiltered. Then, in an oil bath at 90° C. under reduced pressure, thetoluene was removed. The yielded amount of the obtained compound was 7.9g, and the yield was 45%. The molecular weight of the obtained compoundwas measured with a GC-MS. Further, ¹H-NMR of the obtained compound wasmeasured. These analysis values are indicated in (1) and (2) below. Fromthese results, it was verified that the obtained compound was CompoundNo. 68.

Analysis Values:

(1) GC-MS m/z: 129 (M+)

(2) ¹NMR (solvent: deuterated benzene) (chemical shift: multiplicity:number of H):

(7.116:s:1), (4.413:s:1), (3.153-3.193:m:2), (1.501-1.573:m:1),(1.347-1.419:m:1), (1.152:s:3), (0.981-1.017:t:3), (0.837-0.875:t:3).

Example 7

Production of Alcohol Compound (Compound No. 76) of Present Invention:

To a reaction flask was added a diethyl ether solution of ethylmagnesiumbromide (39%, 16 g), and this was stirred over an ice-cooled bath andcooled to around 0° C. To this solution, 3,3-dimethoxy-2-butanone (6.19g) was added dropwise in 1 hour, and the solution was subjected to aGrignard reaction. Then, the solution was returned to room temperature,and was subjected to reaction for 12 hours. The reaction solution wascooled on ice, and then 75 g of a 20% ammonium chloride aqueous solutionwas added dropwise, and then 3 ml of a 36% hydrochloric acid solutionwas added dropwise, and the mixture was stirred overnight. Only theorganic layer was separated and recovered, and then 18.5 g of a 33%ethylamine aqueous solution was added thereto dropwise while cooling onice, and the mixture was subjected to reaction for 20 hours. At thistime, the pH of the reaction solution was from 10 to 11. The reactionsolution was dehydrated by adding magnesium sulfate and was filtered,and then desolventization was performed in an oil bath at 60° C. underreduced pressure. Distillation was performed in an oil bath at 80° C. ata pressure of 300 Pa. The obtained compound was a colorless transparentliquid, and the yielded amount was 2.3 g, and the yield was 34%. Themolecular weight of the obtained compound was measured with a GC-MS.Further, ¹H-NMR of the obtained compound was measured. These analysisvalues are indicated in (1) and (2) below. From these results, it wasverified that the obtained compound was Compound No. 76.

Analysis Values:

(1) GC-MS m/z: 143.23 (M+)

(2) ¹NMR (solvent: deuterated benzene) (chemical shift: multiplicity:number of H):

(5.85:s:1), (2.948-3.003:q:2), (1.602-1.692:m:1), (1.379-1.475:m:1),(1.254:s:3), (1.223:s:3), (1.040-1.077:t:3), (0.826-0.863:t:3).

Production Example 1

Production of Alcohol Compound 1:

In a reaction flask, a tetrahydrofuran solution of methylamine (2 M, 200ml) was cooled on ice, and 24 g of 3-hydroxy-3-methyl-2-butanone wasadded thereto dropwise, and the mixture was subjected to reaction at aliquid temperature of around 10° C. Then, the mixture was returned toroom temperature and was stirred for 8 hours. A suitable amount ofmagnesium sulfate was added to adsorb the water in the solution, and thesolution was filtered. A sufficiently dried molecular sieve 4A was addedto the filtrate to completely dehydrate the filtrate. The molecularweight of the obtained compound was measured with a GC-MS. Also, anelementary analysis of the obtained compound was performed. Theseanalysis values are indicated in (1) and (2) below. From these results,it was verified that the obtained compound was the following alcoholcompound 1. Note that the yield of the compound was 49%.

Analysis Values:

(1) GC-MS m/z: 115 (M+)

(2) Elementary Analysis: C: 61.7 mass %; H: 11.3 mass %; O: 13.9 mass %;N: 12.2 mass % (theoretical values: C: 62.6%; H: 11.3%; O: 13.9%; N:12.2%).

Example 8

Production of Metal Alkoxide Compound (Compound No. 25) of PresentInvention:

To a reaction flask were added 1.2 g of copper (II) methoxide and 20 gof dehydrated toluene and these were made into a suspension. To thissuspension, 18 g of a 15 wt. % tetrahydrofuran solution of the alcoholcompound 1 obtained in Production Example 1 was added dropwise at roomtemperature in an argon gas atmosphere. After stirring for 1 hour, thesolution gradually turned purple, and was kept stirred at roomtemperature for 10 hours. Then, the tetrahydrofuran was removed byevaporation in an oil bath at a temperature of 85° C., and then,solvents such as toluene were removed by evaporation in an oil bath at atemperature of 120° C. under slightly reduced pressure. The obtainedpurple solid was sublimed at 110° C. at 40 Pa, to obtain the targetproduct. The obtained compound was a solid having a melting point of195° C. The yield of the compound was 50%. The obtained compound was acompound exhibiting no spontaneous ignitability. The obtained compoundwas subjected to single-crystal X-ray structural analysis. FIG. 5illustrates a molecular structure diagram obtained by the single-crystalX-ray structural analysis. From this result, it was verified that theobtained compound was Compound No. 25. Further, the obtained compoundwas subjected to TG-DTA measurement under atmospheric pressure or underreduced pressure. These analysis values are indicated in (1) and (2)below.

Analysis Values:

(1) Atmospheric Pressure TG-DTA

50% mass reduction temperature: 205° C. (Ar flow rate: 100 ml/min.;temperature rise: 10° C./min.)

(2) Reduced Pressure TG-DTA

50% mass reduction temperature: 154° C. (pressure: 10 Torr; Ar flowrate: 50 ml/min.; temperature rise: 10° C./min.)

Example 9

Production of Metal Alkoxide Compound (Compound No. 41) of PresentInvention:

To a reaction flask were added 6.01 g of hexaamminenickel (II) chlorideand 39.00 g of tetrahydrofuran, and the mixture was stirred at roomtemperature. To this mixture was added dropwise, at room temperature, asolution in which 7.30 g of a sodium alkoxide obtained by reactingsodium and the alcohol compound 1, which was obtained in ProductionExample 1, was suspended in 24 g of tetrahydrofuran. After completion ofthis dropwise addition, the solution was stirred at room temperature for2 hours, and was then refluxed for 7 hours. Then, the solution was leftto cool at room temperature, was then stirred for 15 hours, and wasfiltered. Tetrahydrofuran was removed from the obtained filtrate, and agreen solid was obtained as the residue. The solid was sublimed underthe conditions of 100 Pa and 120° C. The yielded amount of the obtainedcompound was 0.98 g, and the yield was 13%. The obtained compound was agreen solid having a melting point of 212° C. The obtained compound wasa compound exhibiting no spontaneous ignitability. The obtained compoundwas subjected to single-crystal X-ray structural analysis. FIG. 6illustrates a molecular structure diagram obtained by the single-crystalX-ray structural analysis. From this result, it was verified that theobtained compound was Compound No. 41. Further, the obtained compoundwas subjected to ¹H-NMR and TG-DTA measurement under atmosphericpressure or under reduced pressure. These analysis values are indicatedin (1), (2), and (3) below.

Analysis Values:

(1) ¹H-NMR (solvent: deuterated benzene) (chemical shift: multiplicity:number of H):

(2.425:s:6), (1.246:s:12), (0.955:s:6).

(2) Atmospheric Pressure TG-DTA

50% mass reduction temperature: 218° C. (Ar flow rate: 100 ml/min.;temperature rise: 10° C./min.)

(3) Reduced Pressure TG-DTA

50% mass reduction temperature: 160° C. (pressure: 10 Torr; Ar flowrate: 50 ml/min.; temperature rise: 10° C./min.)

Example 10

Production of Metal Alkoxide Compound (Compound No. 47) of PresentInvention:

In a reaction flask were placed 5.08 g of hexaamminenickel (II) chlorideand 15 g of tetrahydrofuran, and the mixture was stirred at roomtemperature. To this mixture was added dropwise, at room temperature, asolution in which 7.10 g of a sodium alkoxide obtained by reactingsodium and Compound No. 74, which was obtained in Example 5, wassuspended in 17 g of tetrahydrofuran. After completion of this dropwiseaddition, the solution was stirred at room temperature for 20 minutes,and was then refluxed for 5 hours. Then, the solution was left to coolat room temperature, was then stirred for 15 hours, and was filtered.Tetrahydrofuran was removed from the obtained filtrate, and a greensolid was obtained as the residue. The solid was sublimed under theconditions of 100 Pa and 100° C. The yielded amount of the obtainedcompound was 4.87 g, and the yield was 65%. The obtained compound was ablackish-brownish solid having a melting point of 155° C. The obtainedcompound was a compound exhibiting no spontaneous ignitability. Theobtained compound was subjected to single-crystal X-ray structuralanalysis. FIG. 7 illustrates a molecular structure diagram obtained bythe single-crystal X-ray structural analysis. From this result, it wasverified that the obtained compound was Compound No. 47. Further, theobtained compound was subjected to ¹H-NMR and TG-DTA measurement underatmospheric pressure or under reduced pressure. These analysis valuesare indicated in (1), (2), and (3) below.

Analysis Values:

(1) ¹H-NMR (solvent: deuterated benzene) (chemical shift: multiplicity:number of H):

(3.774:sept:2), (1.444:d:12), (1.184:s:12), (1.060:s:6).

(2) Atmospheric Pressure TG-DTA

50% mass reduction temperature: 203° C. (Ar flow rate: 100 ml/min.;temperature rise: 10° C./min.)

(3) Reduced Pressure TG-DTA

50% mass reduction temperature: 140° C. (pressure: 10 Torr; Ar flowrate: 50 ml/min.; temperature rise: 10° C./min.)

Example 11

Production of Metal Alkoxide Compound (Compound No. 57) of PresentInvention:

In a reaction flask were placed 3.50 g of cobalt (II) chloride and 20 gof tetrahydrofuran, and the mixture was stirred at room temperature. Tothis mixture was added dropwise, at room temperature, a solution inwhich 7.11 g of a sodium alkoxide obtained by reacting sodium and thealcohol compound 1, which was obtained in Production Example 1, wassuspended in 10 g of tetrahydrofuran. After completion of this dropwiseaddition, the solution was stirred for 23 hours at room temperature, andwas filtered. Tetrahydrofuran was removed from the obtained filtrate,and a dark brown solid was obtained as the residue. The solid wassublimed under the conditions of 80 Pa and 145° C. The yielded amount ofthe obtained compound was 0.91 g, and the yield was 13%. The obtainedcompound was an orange solid having a melting point of 220° C. Theobtained compound was a compound exhibiting no spontaneous ignitability.The obtained compound was subjected to single-crystal X-ray structuralanalysis. FIG. 8 illustrates a molecular structure diagram obtained bythe single-crystal X-ray structural analysis. From this result, it wasverified that the obtained compound was Compound No. 57. Further, theobtained compound was subjected to TG-DTA measurement under atmosphericpressure or under reduced pressure. These analysis values are indicatedin (1) and (2) below.

Analysis Values:

(1) Atmospheric Pressure TG-DTA

50% mass reduction temperature: 219° C. (Ar flow rate: 100 ml/min.;temperature rise: 10° C./min.)

(2) Reduced Pressure TG-DTA

50% mass reduction temperature: 166° C. (pressure: 10 Torr; Ar flowrate: 50 ml/min.; temperature rise: 10° C./min.)

Example 12

Production of Metal Alkoxide Compound (Compound No. 63) of PresentInvention:

In a 200-ml four-neck flask were placed 2.79 g of cobalt (II) chlorideand 22 g of tetrahydrofuran, and the mixture was stirred at roomtemperature. To this mixture was added dropwise, at room temperature, asolution in which 6.46 g of a sodium alkoxide obtained by reactingsodium and Compound No. 74, which was obtained in Example 5, wassuspended in 10 g of tetrahydrofuran. After completion of this dropwiseaddition, the solution was stirred for 22 hours at room temperature, andwas filtered. Tetrahydrofuran was removed from the obtained filtrate,and a green solid was obtained as the residue. This solid was sublimedunder the conditions of 80 Pa and 100° C. The yielded amount of theobtained compound was 2.24 g, and the yield was 34%. The obtainedcompound was a green solid having a melting point of 145° C. Theobtained compound was a compound exhibiting no spontaneous ignitability.The obtained compound was subjected to single-crystal X-ray structuralanalysis. FIG. 9 illustrates a molecular structure diagram obtained bythe single-crystal X-ray structural analysis. From this result, it wasverified that the obtained compound was Compound No. 63. The obtainedcompound was subjected to TG-DTA measurement under atmospheric pressureor under reduced pressure. These analysis values are indicated in (1)and (2) below.

Analysis Values:

(1) Atmospheric Pressure TG-DTA

50% mass reduction temperature: 227° C. (Ar flow rate: 100 ml/min.;temperature rise: 10° C./min.)

(2) Reduced Pressure TG-DTA

50% mass reduction temperature: 149° C. (pressure: 10 Torr; Ar flowrate: 50 ml/min.; temperature rise: 10° C./min.)

Evaluation Example 1

Evaluation of Physical Properties of Alkoxide Compound:

For each of Compounds Nos. 25, 41, 47, 57, and 63 of the presentinvention obtained in Examples 8-12 and the following ComparativeCompounds 1, 2, and 3, the temperature at which the sample weight wasreduced by 50 mass % by heating in a reduced-pressure atmosphere (10torr) was verified by using a TG-DTA measurement device (thistemperature may be abbreviated below as TG 50% reduction temperature).Further, by measuring the temperature at which thermal decompositionoccurs by using a DSC measurement device, the thermal stability of eachcompound was verified. The results are shown in Table 1.

TABLE 1 Thermal TG 50% decomposition Evaluation reduction occurrenceExample Compound temperature (° C.) temperature (° C.) Comp. EvaluationComp. 165 210 Example 1-1 Compound 1 Comp. Evaluation Comp. 110 290Example 1-2 Compound 2 Comp. Evaluation Comp. 155 220 Example 1-3Compound 3 Evaluation Compound 150 230 Example 1-1 No. 25 EvaluationCompound 160 330 Example 1-2 No. 41 Evaluation Compound 140 320 Example1-3 No. 47 Evaluation Compound 165 290 Example 1-4 No. 57 EvaluationCompound 150 300 Example 1-5 No. 63

From the results in Table 1, when Compound No. 25 was compared withComparative Compound 1 which is a copper tertiary-aminoalkoxide compoundhaving a similar structure, it was found that Compound No. 25 had a lowTG 50% reduction temperature and a high thermal decompositiontemperature. When Compounds Nos. 41 and 47 were compared withComparative Compound 2 which is a nickel tertiary-aminoalkoxide compoundhaving a similar structure, it was found that Compounds Nos. 41 and 47had significantly-improved thermal decomposition temperatures thatgreatly exceeded 300° C., although Comparative Compound 2 had a slightlylower TG 50% reduction temperature. When Compounds Nos. 57 and 63 werecompared with Comparative Compound 3 which is a cobalttertiary-aminoalkoxide compound having a similar structure, it was foundthat Compounds Nos. 57 and 63 had significantly-improved thermaldecomposition temperatures, although there was no significant differencein TG 50% reduction temperature. From the above, it was found that thecompounds of the present invention have vapor pressures that are thesame as or higher than conventional products and also have higherthermal decomposition temperatures, and are thus particularly suitableas CVD materials.

Example 13

Production of Metal Alkoxide Compound (Compound No. 17) of PresentInvention:

In an argon gas atmosphere, a mixed solution of Compound No. 65 obtainedin Example 1 and 400 ml of diethyl ether was added slowly dropwise to7.45 g of copper (II) methoxide while cooling on ice. Then, the solutionwas returned to room temperature, and was subjected to reaction forabout 17 hours. Then, diethyl ether was removed by evaporation in a bathat 58° C. under atmospheric pressure, to obtain a dark purple crystal.Then, 350 ml of hexane was added and the mixture was heated in a bath at56° C., to dissolve the crystal. The obtained solution was thermallyfiltered with a 0.2-μm membrane filter, and was recrystallized, toobtain a dark purple crystal. The recovery rate by this refinement was37%. The obtained compound was a solid having a melting point of 165° C.The obtained compound was a compound exhibiting no spontaneousignitability. The obtained compound was subjected to single-crystalX-ray structural analysis. FIG. 10 illustrates a molecular structurediagram obtained by the single-crystal X-ray structural analysis. Fromthis result, it was verified that the obtained compound was Compound No.17. Further, the obtained compound was subjected to TG-DTA measurementunder atmospheric pressure or under reduced pressure. These analysisvalues are indicated in (1) and (2) below.

Analysis Values:

(1) Atmospheric Pressure TG-DTA

50% mass reduction temperature: 173° C. (Ar flow rate: 100 ml/min.;temperature rise: 10° C./min.)

(2) Reduced Pressure TG-DTA

50% mass reduction temperature: 121° C. (pressure: 10 Torr; Ar flowrate: 50 ml/min.; temperature rise: 10° C./min.)

Example 14

Production of Metal Alkoxide Compound (Compound No. 18) of PresentInvention:

In an argon gas atmosphere, a mixed solution of Compound No. 66 obtainedin Example 2 and 80 ml of toluene was added slowly dropwise to 1.60 g ofcopper (II) methoxide while cooling on ice. Then, the solution wasreturned to room temperature, and was subjected to reaction for about 20hours. Then, toluene was removed by evaporation under reduced pressurein a bath at 94° C., to obtain a dark purple crystal. This solid wassublimed under reduced pressure at 83° C. in a glass tube oven, toobtain a purple crystal. The obtained compound was a solid having amelting point of 103° C. The yield of the obtained compound was 43%. Theobtained compound was a compound exhibiting no spontaneous ignitability.The obtained compound was subjected to single-crystal X-ray structuralanalysis. FIG. 11 illustrates a molecular structure diagram obtained bythe single-crystal X-ray structural analysis. From this result, it wasverified that the obtained compound was Compound No. 18. Further, theobtained compound was subjected to TG-DTA measurement under atmosphericpressure or under reduced pressure. These analysis values are indicatedin (1) and (2) below.

Analysis Values:

(1) Atmospheric Pressure TG-DTA

50% mass reduction temperature: 169° C. (Ar flow rate: 100 ml/min.;temperature rise: 10° C./min.)

(2) Reduced Pressure TG-DTA

50% mass reduction temperature: 116° C. (pressure: 10 Torr; Ar flowrate: 50 ml/min.; temperature rise: 10° C./min.)

Example 15

Production of Metal Alkoxide Compound (Compound No. 19) of PresentInvention:

In an argon gas atmosphere, a mixed solution of Compound No. 67 obtainedin Example 3 and 50 ml of diethyl ether was added slowly dropwise, whilecooling on ice, to a mixed solution of 0.65 g of copper (II) methoxideand 30 ml of hexane. Then, the solution was returned to roomtemperature, and was subjected to reaction for about 16 hours. Then,diethyl ether was removed by evaporation in a bath at 70° C. underatmospheric pressure, to obtain a dark purple crystal. This solid wassublimed under reduced pressure at 83° C. in a glass tube oven, toobtain a purple crystal. The yield of the obtained compound was 38%. Theobtained compound was a compound exhibiting no spontaneous ignitability.The obtained compound was subjected to single-crystal X-ray structuralanalysis. FIG. 12 illustrates a molecular structure diagram obtained bythe single-crystal X-ray structural analysis. From this result, it wasverified that the obtained compound was Compound No. 19. Further, theobtained compound was subjected to TG-DTA measurement under atmosphericpressure or under reduced pressure. These analysis values are indicatedin (1) and (2) below.

Analysis Values:

(1) Atmospheric Pressure TG-DTA

50% mass reduction temperature: 170° C. (Ar flow rate: 100 ml/min.;temperature rise: 10° C./min.)

(2) Reduced Pressure TG-DTA

50% mass reduction temperature: 116° C. (pressure: 10 Torr; Ar flowrate: 50 ml/min.; temperature rise: 10° C./min.)

Example 16

Production of Metal Alkoxide Compound (Compound No. 20) of PresentInvention:

In an argon gas atmosphere, 42 g of a 4.24 wt. % toluene solution ofCompound No. 68, which was obtained in Example 6, was added dropwise to0.786 g of copper (II) methoxide. The solute dissolved immediately andexhibited a purple color, but the solution was kept stirred at roomtemperature for 17 hours. Toluene was removed by evaporation in an oilbath at a temperature of 70° C. under slightly reduced pressure, andthen, the remaining toluene was completely removed by evaporation in anoil bath at a temperature of 90° C. under reduced pressure. The obtainedpurple solid was distilled at 100° C. at 40 Pa, to obtain the targetproduct. The obtained compound was a solid having a melting point of 58°C. The yield of the compound was 48%. The obtained compound wassubjected to single-crystal X-ray structural analysis. FIG. 13illustrates a molecular structure obtained by the single-crystal X-raystructural analysis. From this result, it was verified that the obtainedcompound was Compound No. 20. Further, the obtained compound wassubjected to TG-DTA measurement under atmospheric pressure or underreduced pressure, and to DSC measurement. These analysis values areindicated in (1), (2), and (3) below.

Analysis Values:

(1) Atmospheric Pressure TG-DTA

50% mass reduction temperature: 174° C. (Ar flow rate: 100 ml/min.;temperature rise: 10° C./min.)

(2) Reduced Pressure TG-DTA

50% mass reduction temperature: 108° C. (pressure: 10 Torr; Ar flowrate: 50 ml/min.; temperature rise: 10° C./min.)

(3) DSC Thermal Decomposition Occurrence Temperature

168° C.

Example 17

Production of Metal Alkoxide Compound (Compound No. 23) of PresentInvention:

In a 100-ml three-neck flask, 20 g of a 15 wt. % ether solution ofCompound No. 71, which was obtained in Example 4, was added dropwise, atroom temperature in an argon gas atmosphere, to a suspension of 1.2 g ofcopper (II) methoxide and 20 g of dehydrated hexane. After stirring for1 hour, the solution gradually exhibited a purple color, and thesolution was kept stirred for 10 hours at room temperature. Ether wasremoved by evaporation in a bath at 50-60° C., and then solvents, suchas hexane, were removed by evaporation in a bath at 110° C. The residuewas sublimed at 110° C. at 40 Pa. The obtained compound was a solidhaving a melting point of 185° C. The yield was 40%. The obtainedcompound was a compound exhibiting no spontaneous ignitability. Theobtained compound was subjected to single-crystal X-ray structuralanalysis. FIG. 14 illustrates a molecular structure diagram obtained bythe single-crystal X-ray structural analysis. From this result, it wasverified that the obtained compound was Compound No. 23. Further, theobtained compound was subjected to TG-DTA measurement under atmosphericpressure or under reduced pressure. These analysis values are indicatedin (1) and (2) below.

Analysis Values:

(1) Atmospheric Pressure TG-DTA

50% mass reduction temperature: 184° C. (Ar flow rate: 100 ml/min.;temperature rise: 10° C./min.)

(2) Reduced Pressure TG-DTA

50% mass reduction temperature: 131° C. (pressure: 10 Torr; Ar flowrate: 50 ml/min.; temperature rise: 10° C./min.)

Example 18

Production of Metal Alkoxide Compound (Compound No. 60) of PresentInvention:

To a reaction flask were added 1.15 g of cobalt-bis-trimethylsilylamideand 20 g of dehydrated toluene, and the mixture was mixed sufficiently.This solution was cooled on ice, and 1.05 g of2-ethylimino-3-methylpentane-3-ol was added dropwise over a period of 5minutes. The solution changed from dark blue to brown. After completionof this dropwise addition, the solution was stirred overnight at roomtemperature. Then, the solution was desolventized under reduced pressurein an oil bath at 100° C., and the produced cobalt complex (brown solid)was sufficiently dried. This cobalt complex was placed in a 50-ml flaskwhich was connected to a sublimation refinement device. Sublimationrefinement was performed in an oil bath at 100-110° C. at 40 Pa, toobtain 0.50 g of a red-brown crystal. The yield of the compound was 53%.The melting point of the obtained solid was 104° C. FIG. 15 illustratesa result of the single-crystal X-ray structural analysis. From thisresult, it was verified that the obtained compound was Compound No. 60.Further, the obtained compound was subjected to TG-DTA measurement underatmospheric pressure or under reduced pressure, and to DSC measurement.These analysis values are indicated in (1), (2), and (3) below.

Analysis Values:

(1) Atmospheric Pressure TG-DTA

50% mass reduction temperature: 211.9° C. (Ar flow rate: 100 ml/min.;temperature rise: 10° C./min.)

(2) Reduced Pressure TG-DTA

50% mass reduction temperature: 128.8° C. (pressure: 10 Torr; Ar flowrate: 50 ml/min.; temperature rise: 10° C./min.)

(3) DSC Thermal Decomposition Occurrence Temperature

315° C.

Evaluation Example 2

Evaluation of Physical Properties of Alkoxide Compound:

For each of Compounds Nos. 17, 18, 19, and 23, which are copper alkoxidecompounds of the present invention obtained in Examples 13 to 15 and 17,and Comparative Compound 1, the temperature at which the sample weightwas reduced by 50 mass % by heating in a reduced-pressure atmosphere (10torr) was verified by using a TG-DTA measurement device. Further, bymeasuring the temperature at which thermal decomposition occurs by usinga DSC measurement device, the thermal stability of each compound wasverified. The results are shown in Table 2.

TABLE 2 Thermal TG 50% decomposition Evaluation reduction occurrenceExample Compound temperature (° C.) temperature (° C.) Comp. EvaluationComp. 165 210 Example 2 Compound 1 Evaluation Compound 120 160 Example2-1 No. 17 Evaluation Compound 115 170 Example 2-2 No. 18 EvaluationCompound 115 170 Example 2-3 No. 19 Evaluation Compound 130 190 Example2-4 No. 23

From the results in Table 2, when Compounds Nos. 17 to 19 and 23(Evaluation Examples 2-1 to 2-4) were compared with Comparative Compound1 (Comparative Evaluation Example 2) having a similar structure, it wasfound that Compounds Nos. 17 to 19 and 23 had significantly lower TG 50%reduction temperatures than Comparative Compound 1. Further, it wasfound that Compounds Nos. 17 to 19 and 23 had thermal decompositionoccurrence temperatures below 200° C., whereas the thermal decompositionoccurrence temperature of Comparative Compound 1 was above 200° C.

From the above, it was found that the copper compounds of the presentinvention are particularly suitable as materials for formingmetallic-copper thin films by CVD.

Example 19

Production of Copper-Oxide Thin Film:

The copper compound (Compound No. 18) of the present invention obtainedin Example 14 was used as a chemical vapor deposition material, and acopper-oxide thin film was produced on a silicon wafer substrate by CVDaccording the following conditions by using the device illustrated inFIG. 3. The obtained thin film was subjected to film-thicknessmeasurement by X-ray reflectometry and to a verification of thin-filmstructure and thin-film composition by X-ray diffractometry and X-rayphotoelectron spectroscopy. The film thickness was 120 nm, and the filmcomposition was copper oxide.

Conditions:

Vaporizing chamber temperature: 50° C.; Reaction pressure: 100 Pa;Reaction time: 60 minutes; Substrate temperature: 150° C.; Carrier gas(Ar): 100 ml/min.; Oxidizing gas (oxygen): 200 ml/min.

Example 20

Production of Metallic-Copper Thin Film:

The copper compound (Compound No. 23) of the present invention obtainedin Example 17 was used as a chemical vapor deposition material, and ametallic-copper thin film was produced on a silicon wafer substrate bythermal CVD according the following conditions by using the deviceillustrated in FIG. 3. The obtained thin film was subjected tofilm-thickness measurement by X-ray reflectometry and to a verificationof thin-film structure and thin-film composition by X-ray diffractometryand X-ray photoelectron spectroscopy. The film thickness was 100 nm, andthe film composition was metallic copper.

Conditions:

Material temperature: 50° C.; Reaction system pressure: 100 Pa; Reactiontime: 60 minutes; Substrate temperature: 185° C.; Carrier gas (Ar): 100ml/min.; Reactive gas: none.

Comparative Example 1

Production of Comparative Metallic-Copper Thin Film:

Comparative Compound 1 was used as a chemical vapor deposition material,and a metallic-copper thin film was produced on a silicon wafersubstrate by thermal CVD according the following conditions by using thedevice illustrated in FIG. 3. The obtained thin film was subjected tofilm-thickness measurement by X-ray reflectometry and to a verificationof thin-film structure and thin-film composition by X-ray diffractometryand X-ray photoelectron spectroscopy. The film thickness was 75 nm, andthe film composition was metallic copper.

Conditions:

Vaporizing chamber temperature: 50° C.; Reaction pressure: 100 Pa;Reaction time: 60 minutes; Substrate temperature: 240° C.; Carrier gas(Ar): 100 ml/min.; Reactive gas: none.

Evaluation Example 3

The metallic-copper thin film obtained by Example 20 was compared withthe comparative metallic-copper thin film obtained by ComparativeExample 1. The results are shown in Table 3.

TABLE 3 Average polycrystalline Electric Deposition rate of particlesize of resistance metallic-copper metallic-copper value (μΩ · thin film(nm/h) thin film (μm) cm) Example 20 100 0.05 2 Comparative 75 0.3 4.2Example 1

From Table 3, when Example 20 was compared with Comparative Example 1,it was found that: Example 20 had a higher metallic-copper thin-filmdeposition rate than Comparative Example 1; the average polycrystallineparticle size of the metallic-copper thin film obtained by Example 20was smaller than the average polycrystalline particle size of thecomparative metallic-copper thin film obtained by Comparative Example 1;and the electric resistance value of the metallic-copper thin filmobtained by Example 20 was more than twice lower than the electricresistance value of the comparative metallic-copper thin film obtainedby Comparative Example 1. From the above, it was found that the presentinvention can provide a metallic-copper thin film having excellentcharacteristics.

The invention claimed is:
 1. An alcohol compound of general formula(II):

wherein, R⁴ represents a methyl group or an ethyl group, R⁵ represents ahydrogen atom, and R⁶ represents a C₁₋₃ linear or branched alkyl group.